Enhancing Zn Deposition Reversibility on MXene Current Collectors by Forming ZnF ₂ ‐Containing Solid‐Electrolyte Interphase for Anode‐Free Zinc Metal Batteries

Abstract Anode‐free aqueous zinc metal batteries (AZMBs) offer significant potential for energy storage due to their low cost and environmental benefits. Ti ₃ C ₂ T _x MXene provides several advantages over traditional metallic current collectors like Cu and Ti, including better Zn plating affinity, lightweight, and flexibility. However, self‐freestanding MXene current collectors in AZMBs remain underexplored, likely due to challenges with Zn deposition reversibility. This study investigates the combination of a Ti ₃ C ₂ T _x self‐freestanding film with advanced electrolyte engineering, specifically examining the effects of Li‐salt and propylene carbonate (PC) as additives on Zn plating reversibility. While using Li ⁺ ions as an additive alone facilitates uniform Zn deposition on bulk metals through the electrostatic shielding effect, the addition of Li‐salt negatively impacts Zn plating uniformity on Ti ₃ C ₂ T _x . Meanwhile, using PC additive alone forms an organic SEI layer on Ti ₃ C ₂ T _x and causes Zn agglomeration. The use of both additives together results in a ZnF ₂ ‐containing hybrid SEI layer with improved interfacial kinetics, promoting more uniform Zn deposition. This approach achieves an average Coulombic efficiency (CE) of 96.8% over 150 cycles (a maximum CE of 97.8%). The study highlights the strategic difference in electrolyte design, emphasizing the need for tailored approaches to optimize Zn deposition on MXenes, contrasting with traditional metallic current collectors.